Process of utilizing gaseous unsaturated hydrocarbons



EAWME Aug. 7, E923.

C. ELLIS PROCESS 0F' UTILIZING GASOUS UNSATURATED HYDROCRBONS Filed June 5, 1918 /1 @imag wlw UDQOML :OCEL

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INVENTUR lltatentedA Aug, l, 'i923a atta-152 PATENT oel-ien cantaron Ennis, or MoNrcLAn'a, naw Jnnsnv, Assmann., nr Mnsnn assicumnn'rs, 'ro sn'rn n. naar, or Mourir xrsco, new ronx, 'inneren 'rnocnss' or U'rrnrzrie ensnous Unsn'runn'rnn nrnnocnnnoiva.

vApplication led .lune 5,

Toall 'whom t may con/cern:

Be it @own that LUARLETON Ennis, a citizen of the United States, and a resident of Montclair, county of Essex, and State o of New Jersey, have invented certainnew` and useful Improvements in Process of Utilizing Gaseous Unsaturated. Hydrocarbons, of which the following is a specification.

'lhis invention relates to the process of utilizin unsaturated hydrocarbons, and is applica 1e more especially to lui'isaturated hydrocarbons in the gaseous or vapcrous state. 1

Graseous or 'vaporous hydrocarbon material containing unsaturated hydrocarbons may be utilized for the purpose of the present' invention, as, for example, the gases and vapors from petroleum cracking stills, 2o gases and vapors of shale oil and the like remaining after condensation of the liquid hydrocarbons, these gases and vapors, being hereinafter designated "as permanent gases.

as ISuch gaseous and vaporous materials are brought into and out of cgntact with an extracting orpolymerizing agent, such, for

' example, as sulfuric acid, which may serve substantially the purposes of a catalyzer for `3o polymerizing unsaturated hydrocarbons,

producing generally higher boiling materials therefrom, and such polymerized ma.- terials, which accompany the escaping gases, are collected from the fixed gases, as,

for example, by absorption in a suitable absorbent liquid or by compression under substantially high pressures with effective condensation, and in various other ways.

A variety of `nieans may be' resorted to e0 for bringing the gases and vapors into andout of contact'A with a liquidl extracting, polymerizing or catalyzing agent, such as sulfuric acid, as, for example, the sulfuric acid may be permitted to flow through a' tower containing lrefractory material such as coke, gravel or the like, through which the gases and vapors are passed in the opposite" direction, or the gases and vapors may. be passed through a receptacle in 5o whicha body of sulfuric acid is kept in violent agitation, or contact with the acid substantially in the forni of films and sprays may be obtained as by passing the gases and vapors through a beater or `siacni- 193.8.. Serial lilo. 338.2711.

acid or other extracting agent, and the character of the extract obtained varies in accordance with the conditions of extraction, as, for example, with some portions of the gases and vapors, if strong acids 'or high temperatures, or both, aroused, considerable quantities of oils are yforrned `which separate out from the acid extract on being permitted to stand, and, more es' pecially, where lower temperatures and weaker acids, or both, are used, an extract may be obtained of such character as that mixtures of alcohols corresponding to unsaturatedhydrocarbcns, such as ol'elines, f

present in the oil gas may) be obtained by hydrolysis. ln general, the lighter the unsaturated components of the gases. vor vapors are, the higher .the temperature and the stronger the acidrwhich may be used for the production of Yacid extract adapted bo give good yields of alcoholic materials.v

'lhe oil gases and vapors, after contact.

ing with the relatively large quantities of sulfuric acid used, enerally entrain more or. less sulfuric acid therewith, and traps, scrubbers and the like may be resorted to for recovery of the entrained acid, whereby the loss' thereof, as vvell as the contamination of the vapors or gases by sulfuric acid, may be substantially prevented. 'llho aciduso recovered vusually contains more or 'less extracted or polymerized hydrocarbon material.

The production of acid extract from gases and vapors suitable for production of alcohols therefrom by hydrolysis-and the production of oils separating out in liquid form from the acid extract do not constitute a part of the present invention, except as they are claimed herein inA connection With the recovery of the valuable materials from the blending with lo'w being sent to the gas container for use for ordinar .illuminating or fuel purposes, are prefera ly treated Vfor the recovery of valuable materials of the general character referred to. This may be accomplished, for example, bypassing the gases, after treatment with sulfuric acid, through an absorbing' agent, such asfanthracene oil, for example, from which the absorbed materiall may be recovered, as, for example, by fractional distillation, and the oil remainlng after such recovered material is .distilled therefrom may be reused for absorption of further quantities of such valuable materials.

Various types of absorptionapparatus, such as towers, scrubbers, &c., may be usedfor Ibringing the gases into extensive contact with the anthracene oil or other 4absorption material and to obtain'eicent absorption,

The gases may be treated in various other ways, as, for example, they may be subjectedV to pressure and thoroughly refrigerated, whereby a quantity of light liquid material may be obtained which is useful j as for grade gasolene to bring it Y up to the proper high standard, or the gases l'may be passed through li ht oil, such as gasolene, kerosene or the lik by which a conl siderable portion of the 'light material is vabsorbed orV retained, or two or more of such modes for recovery of the valuable material carried by the es pin gases may be resorted to in succession if ldesired, or other suit- .able means may be taken-for the recoveryv Vof suchvaluable material before the gases for burning pur are sentzto the gas condenserfor burning.

An important iield of Aapplication of the presentsinvention'` is found in connection with the production of gasolene by cracking suitable materiah'sucli asheavyfptroleum oils, for example. A `draw-back` of such cracking treatment l is the productiom. in large quantities, of wild gas and light fixed gScS whichare a source of lossinasmuch as they can be utilized substantially only es .and are not readily transportable, as4 1n thecase of liquid hydrocarbon'materlal. The present invention af-v fords a means of saving important quanti- 4ties of such-materials .whichI 'would-- other- Wise be substantially lost, andfoperates, .to mextent at: least, to sulaita xiiilly perform naa-aua "fornexample, to produce substantia y good quality and 'utilizable gasolene therefrom, or such materials may, of course, be made use of for other purposes requiring hlghly volatile material, such: as a primer for in- SQ' I ternal combustion engines, for carburetting oils and for other purposes'commanding relatively high prices. 'It is, of course, common either to pass the gases and vapors, produced in cracking and .which go through the condensers in such form, into absorbent oils and to subject such gases and vapors to pressure .in gas compression apparatus, but so far as I am aware sthe gases and vapors so treated come sub- 90 stantially directly from the cracking stills to 'the absorption or compression apparatus and are not given the intermediate extrac-l tion or polymerizing treatment above de scribed. .95 The present invention does not embrace the production of lubricating or other heavy oils bysulfuric acid polymerization, lthis being the subject of a co-pending applicatio" Serial to which l am a party but relates .especially tothe polymerization step. involving the production of relatively volatile bodies such as gasolene, as set forth above.

The term finely divided? referring to 15 the sulphuric acid as used in the'claims is intended to over'the treatment otherwise referred to as into and out of contact with sulphuric acid. The treatments thus vari-t ously covered are such as are set forth the fifth paragraph of the specification.,V While sulphuric acid has been-used in the claims as an example ofv @a polymerizing agent which may be used in these processes, it is to be understood that other polymerizg agents'may be used in place of the sulphuric acid. Y e The accompanying drawing is a diagrammatical illustrationof one mode of carrying out the invention. The permanent or wild gases fromgcracking operations carried on in the cracking apparatus l() and remaining uncondensed in condenser 11, are brought. into and out ofcontact with sulfurie acid in the acid contacting appara- `tus 12, and after assing through an acid trap13,arescrub d inA sctubbers, as 14, removing, polymerized products of olefines, after whichv ,the gases are com No. 156,197, filed Mar. 2Q, 1917,

` inanent gases polymerized products are obtained by conipression and refrigeration in reirigerating apparatus' le, whence the remaining perpass tothe gas holders.A lclaiin:y e l. 'lhe process of producing light, volatile oils .which comprises contacting gaseous or vaporous hydrocarbon material containing unsaturated hydrocarbons with large vopuantities of hnely divided sulphuric acid whereby polymerization is eected to produce light, volatile oils.v 2. rl`he process of producing light volatile oils which comprises bringing gaseous or vaporoushydrocarbon material containing unsaturated hydrocarbons into 4contact; with lfinely divided sulphuricl acid .Where by polymerization is eected to produce light, volatile oils, and then recovering .the

liquid, polymerized hydrocarbons from the' gases and vapors subsequent to such contact.'

tile oils which comprises bringing permanently gaseous and va orous hydrocarbons containing unsaturat hydrocarbons into contact with nely divided sulphuric acid whereby polymerization is eected tov pro- I duce light, volatile oils and subjecting the gases and vapors so treated to the action of an absorbing agent.

d. 'iF tile oils which comprises bringing vapors 3. The process oi producing light, vola-- he process of producing light .vola.

or gases hum cracMng stills contact withY tinelydivided sulphuric acid whereby polymerization is eected to produce light volatile oils, and then subjectin the ses and vapors alter treatment Wit sulp uric acid9 to condensation under pressure tor recovery of materials adapted thereby to be then collecting and recovering the polyinerized material from the gases andl vapors.

d. The process of producing light, volatileliquid hydrocarbon materialwhich conbringing permanently gaseous hydro sists in carbonet comprising unsaturated hydrocarbons into contact. with finely divided sultill phuric acid-whereby polymerization oi unsaturated hydrocarbons is edectedto produce'light, volatile liquid hydrocarbon material and thensubjecting the hydrocarbons to the action oan absorbing agent and to condensation under pressure.

In testimony that l claiinthe tore oing duna? wld.

l have hereto setiny hand, this lst ay of caanaroa annie. 

